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Mechanism of Post-Radiation-Chemical Graft Polymerization of Styrene in Polyethylene

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Mechanism of Post-Radiation-Chemical Graft Polymerization of Styrene in Polyethylene polymers Article Mechanism of Post-Radiation-Chemical Graft Polymerization of Styrene in Polyethylene Anatoly E. Chalykh 1,*, Vladimir A. Tverskoy 2, Ali D. Aliev 1, Vladimir K. Gerasimov 1, Uliana V. Nikulova 1 , Valentina Yu. Stepanenko 1 and Ramil R. Khasbiullin 1 1 Frumkin Institute of Physical Chemistry and Electrochemistry of Russian Academy of Sciences, Leninsky pr. 31-4, 119071 Moscow, Russia; [email protected] (A.D.A.); [email protected] (V.K.G.); [email protected] (U.V.N.); [email protected] (V.Y.S.); [email protected] (R.R.K.) 2 Lomonosov Institute of Fine Chemical Technologies, MIREA—Russian Technological University, Vernadsky Avenue 78, 119454 Moscow, Russia; [email protected] * Correspondence: [email protected] Abstract: Structural and morphological features of graft polystyrene (PS) and polyethylene (PE) copolymers produced by post-radiation chemical polymerization have been investigated by methods of X-ray microanalysis, electron microscopy, DSC and wetting angles measurement. The studied samples differed in the degree of graft, iron(II) sulphate content, sizes of PE films and distribution of graft polymer over the polyolefin cross section. It is shown that in all cases sample surfaces are enriched with PS. As the content of graft PS increases, its concentration increases both in the volume and on the surface of the samples. The distinctive feature of the post-radiation graft poly- merization is the stepped curves of graft polymer distribution along the matrix cross section. A probable reason for such evolution of the distribution profiles is related to both the distribution of Citation: Chalykh, A.E.; Tverskoy, V.A.; Aliev, A.D.; Gerasimov, V.K.; peroxide groups throughout the sample thickness and to the change in the monomer and iron(II) salt Nikulova, U.V.; Stepanenko, V.Y.; diffusion coefficients in the graft polyolefin layer. According to the results of electron microscope Khasbiullin, R.R. Mechanism of investigations and copolymer wettability during graft polymerization, a heterogeneous system is Post-Radiation-Chemical Graft formed both in the sample volume and in the surface layer. It is shown that the melting point, glass Polymerization of Styrene in transition temperature and degree of crystallinity of the copolymer decreases with the increasing Polyethylene. Polymers 2021, 13, 2512. proportion of graft PS. It is suggested that during graft polymerization a process of PE crystallite https://doi.org/10.3390/ decomposition (melting) and enrichment of the amorphous phase of graft polymer by fragments of polym13152512 PE macromolecules occurs spontaneously. The driving force of this process is the osmotic pressure exerted by the phase network of crystallites on the growing phase of the graft PS. Academic Editor: Shazed Aziz Keywords: post effect radiation graft polymerization; alkoxyradicals; graft polymer distribution Received: 1 July 2021 profile; morphology; graft polymer structure; degree of crystallinity; graft polymer melting Accepted: 26 July 2021 Published: 30 July 2021 Publisher’s Note: MDPI stays neutral 1. Introduction with regard to jurisdictional claims in published maps and institutional affil- Graft polymerization is one of the effective methods for modifying the colloidal– iations. chemical, physical–chemical and performance properties of polymeric materials. Depending on the nature of the monomer, the conditions of graft polymerization and the degree of graft, it is possible to modify the surface layers of polymer material, its volume, and the uniform or gradient distribution of graft polymer over the thickness of a polymer matrix [1–4]. Copyright: © 2021 by the authors. Radiation graft polymerization allows the introduction of functional groups into poly- Licensee MDPI, Basel, Switzerland. mers of various kinds by the direct graft polymerization of monomers, such as acrylic This article is an open access article acid [1,5], vinylpyridines [6,7], acrylonitrile and others [8], or by the subsequent chemical distributed under the terms and modification of graft polymers [5,9,10]. The latter include PS, the chemical modification conditions of the Creative Commons of which allows the introduction of a wide range of functional groups into its struc- Attribution (CC BY) license (https:// ture. Radiation graft polymerization on low density polyethylene (LDPE) is the most creativecommons.org/licenses/by/ studied [1,5,8,11,12]. 4.0/). Polymers 2021, 13, 2512. https://doi.org/10.3390/polym13152512 https://www.mdpi.com/journal/polymers Polymers 2021, 13, 2512 2 of 18 Among various methods of graft polymerization [3], such as “direct” graft, “post effect” graft under irradiation of polymer in a vacuum, inert atmosphere or in air, the “post effect” radiation graft polymerization under irradiation of polymer in air is characterized by its simplicity and high reproducibility. In this case, the polymerization is initiated by alkoxy radicals generated during the decomposition of hydro- and diperoxides. As a rule, salts of variable valence metals are added to the monomer solution as peroxide reducing agents to lower the polymerization temperature. Usually these are iron(II) salts [1,8]. In [9,13–16], sulfonated membranes obtained by such a method of graft polymerization of styrene on PE film for CO2/N2, alkane/olefin mixtures separation and proton conducting membranes for fuel cells are used. However, currently, the studies on influence of graft polymerization parameters on the distribution of graft PS over the cross section of the polymer matrix on PE films of different thicknesses irradiated in air are almost absent. Previously, such studies were carried out only for thin (up to 20 µm) PE films [6,17]. This information is of fundamental importance in the development of technology for the manufacture of asymmetric hybrid membranes for gas separation, namely, when choosing a mathematical model of hybrid membranes. This work presents the results of an investigation of the effects of the phase structure, morphology and distribution of graft PS in LDPE films up to 200 µm thick on “post effect” radiation graft polymerization in a wide range of graft degrees (composition of graft polymer). The results of the studies of the phase structure of graft PS in LDPE presented in this work allow us to specify more exactly the mechanism of styrene post-polymerization in a polyethylene matrix. 2. Experimental Industrial LDPE films with Mw of 49 kDa, Mw/Mn = 11.4 and a refractive index at 130 ◦C of 1.4386 (NizhnekamskOrgSintez Inc., Nizhnekamsk, Russia) were used as objects of the study. The thickness of the films varied, ranging from 20 to 200 µm, and the size of the films was 2 × 5 cm. The samples were not treated before irradiation. The inhibitor was removed from styrene by 30% aqueous solution of KOH, and then washed with water to pH 7, dried over calcium chloride and distilled twice in a vacuum [1,5]. The PE samples were irradiated using a 60Co K-300.500 γ-radiation source at dose rates of 0.0043 Gy/s and from 10 to 100 kGy. The irradiation was performed in air at room temperature. The samples were washed with toluene to constant mass at the end of graft polymerization. Radiation–chemical graft polymerization of styrene in LDPE samples was carried out by the “post effect” method from a mixture of monomer with methanol. Polymerization was carried out in an open ampoule equipped with a thermoelectric cooler. The process temperature was 80 ◦C and was due to the boiling point of the solution containing iron(II) sulfate. As a rule, in this irradiation method, metal salts of variable valence are added as peroxide reducing agents to the monomer solution to reduce the temperature of polymer- ization [18]. These are usually iron(II) salts [19]. At the end of graft, the films were washed of monomer, homopolymer and iron salts by successive soaking in toluene and methanol and were then air dried to constant mass. The amount of graft PS (DP) was determined by gravimetry as film weight gain (Dm) per unit mass of the original PE film (m0) (g of graft PS per mass of PE film): (m − m ) DP = 1 0 × 100%. (1) m0 The characteristics of the studied objects are shown in Table1. Polymers 2021, 13, 2512 3 of 18 Table 1. Characteristics of PE films with graft PS. Composition of Composition of Amount of Graft PS Graft Polymer, Amount of Graft PS Graft Polymer, Sample Sample (g PS/100 g PE) PS Mass Fraction (g PS/100 g PE) PS Mass Fraction (!PS) (!PS) PE/PS16 16 0.14 PE/PS248 248 0.71 PE/PS26 26 0.20 PE/PS271 271 0.73 PE/PS47 47 0.32 PE/PS348 348 0.78 PE/PS96 96 0.49 PE/PS405 405 0.80 EPR spectra were taken on a standard radio spectrometer RE-1306 (Chernogolovka, Russia). The distribution of oxygen-containing compounds throughout the PE film thickness, including peroxide formation, was determined using a comparative analysis of the optical density of 1720 cm−1 band (C=O valence vibrations in oxidized PE [8]) versus the optical density of 1475 cm−1 band (C–H asymmetric deformation vibrations in PE [5]) taken as an internal standard in IR transmission and attenuated total reflection (ATR) spectra. IR spectra were recorded on Perkin–Elmer-580 spectrophotometers (Stockholm, Sweden). ATR spectra were obtained using a KRS-5 crystal with an incidence angle of 45◦ and a scanning depth of ~5 µm. Selective contrasting (sulfonation) of graft polystyrene chains was carried out at a temperature of 98 ◦C with concentrated (96 wt.%) sulfuric acid. At the end of the process, the films were washed with sulphuric acid solutions of decreasing concentrations and distilled water. Sulfonation with a chlorosulfonic acid complex with 1,4-dioxane was carried out in 1,2-dichloroethane at room temperature. The films were then boiled in distilled water to convert the sulphochloride groups to sulphonic acid groups, washed in distilled water and air dried.
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